JP2604221B2 - Photosensitive element for diffusion transfer method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a photosensitive element for a diffusion transfer method.

In particular, the present invention relates to a silver halide photographic light-sensitive element for color diffusion transfer containing a novel yellow dye-providing compound.

(Background Art) In diffusion transfer method photography, as a dye-donating compound,
A compound in which a dye compound portion and a diffusivity conversion portion are bonded is used. The diffusivity converting portion is a portion having a function of changing the diffusibility of the dye-providing compound before and after the development processing under alkaline conditions. Dye-donating compounds are classified into dye-releasing dye-donating compounds and dye-fixing dye-donating compounds according to the function of the diffusivity converting moiety.

Dye-releasing dye-donating compounds are non-diffusible in nature, but release diffusible dyes in response to or reverse development as a result of development under alkaline conditions due to the function of the diffusible conversion part. I do. Many examples of such a dye-releasing dye-releasing compound are known, and are roughly classified into a negative-working nucleus that releases a dye by oxidation and a positive-working nucleus that releases a dye by reduction.

Examples of negative-working dye-providing compounds include JP-A-48-33
826, 49-114424, 49-126331, 49-12633
No. 2, 50-115528, 51-104343, U.S. Pat.
No. 12, No. 3931144, No. 3954476, and Research Disclosure "Research Disclosure", Vol. 130, No. 13024
(Issued in February 1975).

U.S. Pat.
4,139,389, or U.S. Patent 4,139,379, U.S. Patent
No. 4,564,577, JP-A-59-185333 and JP-A-57-84453, the electron acceptability of a compound which releases a photographic reagent by an intramolecular nucleophilic substitution reaction after reduction. What corresponds to the part containing the center and the intramolecular nucleophilic substitution reaction center. U.S. Pat.No.4,232,107, JP-A-59-101649,
As disclosed in Research Disclosure (1984) IV No. 24025 or JP-A-61-88257, the electron acceptability of a compound which releases a photographic reagent by an intramolecular electron transfer reaction after reduction. And a portion containing a carbon atom linking the quinonoid center to the photographic reagent. Also, OLS 3,008,588, JP-A-56-14
No. 2530, U.S. Pat.Nos. 4,343,893 and 4,619,884, an aryl group substituted with an electron-withdrawing group and a photographic reagent in a compound in which a single bond is cleaved after cleavage to release a photographic reagent after reduction. A substance corresponding to a portion containing a connecting atom (sulfur atom, carbon atom, or nitrogen atom). As disclosed in U.S. Pat.No.4,450,223, those corresponding to a nitro group in a nitro compound which releases a photographic reagent after electron acceptance and a portion containing a carbon atom linking the nitro group to the photographic reagent, and U.S. Pat. Examples include the dieminal dinitro moiety in the dinitro compound that β-eliminates the photographic reagent after the described electron acceptance and the one corresponding to the moiety containing a carbon atom linking it to the photographic reagent.

European patent 220,746A for further enhancing its performance
No. 4,783,396, JP-A-87-6199, JP-A-62-215270, JP-A-62-244048, JP-A-63-201653
Nos. 63-201654, 63-271344, 63-271341
NX in the molecule described in Japanese Patent Application No. 62-106885.
Compounds having a bond represented by a bond (X represents oxygen, sulfur, nitrogen) and an electron-accepting group have been found.

The dye-fixing type dye-providing compound is naturally diffusible (or emits a diffusible dye), but becomes non-diffusible (or diffused) by the function of the diffusible conversion part as a result of development processing. Compounds that do not release sex dyes). Examples of such dye-fixing type dye-providing compounds include those described in JP-A-51-63618 and JP-A-53-35,533.

On the other hand, much research has been continued on the dye compound portion of these dye-donating compounds from the viewpoints of hue, transferability, and fastness.

 Examples of yellow are listed below.

U.S. Patent Nos. 3,597,200, 3,309,199, 4,013,633
Nos. 4,245,028, 4,156,609, 4,139,383,
4,195,992, 4,148,641, 4,148,643, 4,3
36,322; JP-A-51-114930, JP-A-56-71072; Resear
ch Disclosure 17630 (1978) and 1645 (1977).

These studies have shown significant improvements in hue, transferability, fastness, and hue stability properties, but they do not sufficiently satisfy the latitude or freedom in the preparation and design of photographic elements. It's hard to say.

In particular, considering the stability of the transferred color image, it does not yet have sufficient performance for both light fading and dark fading, and a more stable dye compound portion has been desired. It is desirable that the stability of the color image is larger, but there is a possibility that the range of use of the diffusion transfer method may be greatly expanded by improving the dye stability.

For example, Japanese Patent Application No. 63-205628 discloses a method of manufacturing a color filter using a diffusion transfer method. The dye in the color filter pattern image needs to have heat resistance and light resistance higher than that of a general diffusion transfer photographic image, but the development of a stable dye further enhances the practical possibility.

(Object of the Present Invention) An object of the present invention is to provide a dye-donating compound which gives first a stable yellow dye image.

Second, it is an object of the present invention to provide a yellow dye-donating compound having a good hue in the dye portion.

Thirdly, it is an object of the present invention to provide a yellow dye-providing compound which gives a transferred image with little change in hue over a wide pH range.

Fourth, it is an object of the present invention to provide a yellow dye-donating compound having improved transferability of a dye portion.

Fifth, the object of the present invention is to provide a diffusion transfer photosensitive element containing a dye-providing compound, which can be used in a method of producing a micro color filter by a diffusion transfer method.

(Constitution of the Invention) As a result of various studies, the present inventors have made the following general formula [I]
It has been found that a color diffusion transfer method photosensitive element containing a 5-aminopyrazoleazo-based yellow dye-donating compound can effectively achieve the above objects.

General formula [I] Wherein CAR represents a carrier component capable of releasing a diffusible dye from the compound under alkaline conditions, corresponding to or inversely corresponding to development. Link represents a group linking CAR and a diffusible dye, and m is 0 or 1. A broken line indicates that at least one of them is connected.

R ¹ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a carbamoyl group, R ² represents an alkyl group, an aryl group, and R ³ represents an aryl group (Excluding aryl groups having a Hammett's σ _p value of less than 0.01).

 The compound of the general formula [I] will be described in more detail.

R ¹ is a hydrogen atom, an alkyl group (including a substituted alkyl group).
Those having up to 10 carbon atoms are preferred. For example, methyl, ethyl, sec-butyl, t-octyl, benzyl, cyclohexyl, chloromethyl, dimethylaminomethyl, n-hexyl, trifluoromethyl, 3,3,3-trichloropropyl, methoxycarbonylmethyl), an aryl group (substituted aryl) For example, phenyl, naphthyl, 3-sulfophenyl, 4-methoxyphenyl, 3-lauroylaminophenyl), an alkoxy group or an aryloxy group (including those having a substituent. Any one having up to 10 carbon atoms) For example, methoxy, ethoxy, propoxy, benzyloxy, phenoxy, 4-methoxyphenoxy, 3-acetylaminophenoxy, 3-methoxycarbonylpropyloxy, 2-trimethylammonioethoxy), an alkoxycarbonyl group or an aryloxy group Xycarbonyl group (including those having a substituent. Those having up to 10 carbon atoms are preferable. For example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 2-methoxyethylcarbonyl, phenoxycarbonyl, 4-cyanophenyl Carbonyl, 2-chlorophenoxycarbonyl) or carbamoyl group (carbon number
Up to 10 are preferred. For example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, methylethylcarbamoyl, phenylcarbamoyl, 2,4,6-trichlorophenylcarbamoyl, N-ethyl-N-phenylcarbamoyl, 3-methylsulfamoylphenylcarbamoyl). .

R ² represents an alkyl group or an aryl group. R ² (Li
nk) Specific examples of the alkyl group and the aryl group of R ² when _m- CAR is not bonded include the alkyl group described for R ¹ ,
This is the same group as the aryl group.

R ³ represents an aryl group (including a substituted aryl group, except for an aryl group having a Hammett's σ _p value of less than 0.01).
Examples of the aryl group of R ³ when (Link) _m -CAR is not bound to R ³ include phenyl, 2-pyridyl, 4-pyridyl, p-nitrophenyl, 4-nitro-2-thiazolyl, p-methyl Sulfonylphenyl, 2-chloro-4-
Nitrophenyl and the like.

In the present invention, the aryl group contains a heterocyclic ring having aromaticity as described above.

Link is the dye compound part in the dye-donating compound and CA
Represents a group connecting to the R moiety, and is bonded to at least one of R ² and R ³ . However, m is 0 or 1.

Link greatly affects the properties (due to hue, diffusivity, mordant, stability, etc.) of the diffusible dye, the overall dye-donating compound (solubility, diffusion resistance, stability, ease of synthesis, etc.), release rate, etc. However, the structure of the dye portion and the CAR portion enables a wide range of structures.

Next, a preferred structure of Link will be described and described with a structure including R ² , R ³ and CAR.

In the general formula [I], -R ² Link _m CAR or -R ³ Link _m CAR is more preferably represented by the following general formula.

In the general formula, X is a divalent linking group represented by the following formula: -R ⁴ -L _n -R ⁴ _p- (wherein R ⁴ may be the same or different,
Alkylene groups each having 1 to about 8 carbon atoms,
L represents a phenylene group or a substituted phenylene group having 6 to about 9 carbon atoms, wherein L represents an oxy group, a carbonyl group, a carboxamide group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfinyl group or a sulfonyl group; 2 chosen
And n is an integer having a value of 0 or 1, and p is 1 when n is 1 and 1 when n is 0.
Or 0; provided that when p is 1, the number of carbon atoms contained in both R ⁴ groups does not exceed 14 in total), and R represents a hydrogen atom Represents or from 1 to about 6 carbon atoms
J represents 2 selected from a sulfone group or a carbonyl group
M and q each represent an integer having a value of 0 or 1; E represents hydrogen, chlorine, bromine, fluorine, an alkyl group having 1 to about 4 carbon atoms or 1 to about carbon atoms; An alkoxy group having 4 carbon atoms, an aryl group having 1 to about 10 carbon atoms, a cyano group, a trifluoromethyl group, a nitro group, an alkylsulfonyl group having 1 to about 8 carbon atoms, a hydroxyl group, a phenyl group, a cyano group An alkylsulfonyl group having 1 to about 8 carbon atoms substituted with a sulfamoyl group, a carboxy group, a fluorosulfonyl group or a sulfo group;
Phenylsulfonyl group or carboxy group, hydroxyl group,
A sulfamoyl group, a fluorosulfonyl group, a phenylsulfonyl group substituted with a carboxoxy group or a sulfo group,
A carboxylate group having the formula: —COOR ⁵ (R ^{5 in the} formula
Is an alkyl group having 1 to about 18 carbon atoms, a phenyl group or a phenyl group substituted with a chlorine or nitro group), a sulfo group, a sulfamoyl group having the formula: —SO ₂ NR ⁶ R ⁷ (wherein , R ⁶ represents a hydrogen atom or an alkyl group having from 1 to about 6 carbon atoms and R ⁷
Is hydrogen, an alkyl group having 1 to about 6 carbon atoms, a hydroxyl group, a cyano group, a fluorosulfonyl group, an alkyl group having 1 to about 6 carbon atoms substituted with a carboxy group or a sulfo group, a benzyl group, a phenyl group A phenyl group substituted with a hydroxyl group, a sulfonyl group, a sulfamoyl group, a carboxy group or a sulfo group, an alkylcarbonyl group having 1 to about 8 carbon atoms or a phenylcarbonyl group having 6 to about 9 carbon atoms; However, the total number of carbon atoms contained in both the R ⁶ group and the R ⁷ group is 14
A carbamoyl group having the formula: CON (R ⁶ ) ₂ (wherein R ⁶ may be the same or different from each other and are the same as defined above), and a carboxy group .

When Link _m CAR is bonded to R ³ , E is selected from the above substituents so that the Hammett's σ _p value is 0 or more.

 Next, the CAR will be described.

CAR is a ballasted, substantially non-diffusible carrier component capable of releasing a diffusible dye from a dye-donating compound of general formula [I] under alkaline conditions or corresponding to development under alkaline conditions. That is, it represents a redox nucleus.

As described above, CAR has roughly a negative action (releases dye in response to development) and a positive action (releases dye in response to development), and any of the CARs in the present invention may be used. Many of the mother nuclei mentioned above correspond to this. Therefore, it can be appropriately selected depending on the use and constitution of the photosensitive element, the structure of the dye component, and the like.

 Next, the CAR will be described in detail.

Much like CAR, the compound of formula (I) is selected to be a non-diffusible image-forming compound that, upon development, is oxidized and self-cleaved to provide a diffusible dye.

An example of a CAR useful for this type of compound is an N-substituted sulfamoyl group. For example, Y can include a group represented by the following formula (YI).

In the formula, β represents a group of non-metallic atoms necessary for forming a benzene ring, and a carbon ring or a hetero ring is fused to the benzene ring, for example, a naphthalene ring, a quinoline ring, 5, 6, 7,
An 8-tetrahydronaphthalene ring, a chroman ring, or the like may be formed.

α represents a group represented by -OG ¹¹ or -NHG ^12. Here G ¹¹ represents a group resulting hydrogen or hydrolyzed to the hydroxyl group, G ¹² represents a hydrogen atom, a group that allows hydrolyze 1-22 alkyl group or NHG ¹² carbon atoms. Ball stands for ballast group. b is 0.1 or 2.

Specific examples of this type of CAR are described in JP-A-48-33826 and JP-A-53-50736.

Another example of a CAR suitable for this type of compound is a group represented by the following formula (YII).

In the formula, Ball, α, b have the same meanings as in formula (YI),
β ′ represents an atomic group necessary for forming a carbocyclic ring, for example, a benzene ring, to which a carbocyclic or heterocyclic ring is further condensed to form a naphthalene ring, a quinoline ring, a 5,6,7,8-
It may form a tetrahydronaphthalene ring, a chroman ring or the like.

Specific examples of the CAR of this ring include U.S. Pat.No.4,055,428, JP-A-56-12642 and JP-A-56-16130, and U.S. Pat.
JP-A-57-4043, JP-A-57-650 and U.S. Pat.
No. 53,312.

Further examples of CARs suitable for this type of compound include:
Examples include groups represented by the following formula (YIII).

In the formula, Ball, α, b are the same as in the case of formula (YI),
β ″ represents an atomic group necessary for forming a hetero ring, for example, a pyrazole ring, a pyridine ring, etc., to which a carbon ring or a hetero ring may be bonded.
Are described in JP-A-51-104343.

Further, the effective CAR for this type of compound is represented by the formula (Y IV)
Some are represented by

In the formula, γ preferably represents a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group or heterocyclic group, or -CO-G ²¹ ; G ²¹ represents -C
O ²² , -S-G ²² or Wherein (G ²² represents a urea, an alkyl group, a cycloalkyl group or an aryl group, G ²³ represents the same group as the G ²² group, or G ²³ represents an aliphatic or aromatic carboxylic acid or a sulfonic acid. Represents an acyl group to be derived,
G ²⁴ represents hydrogen or an unsubstituted or substituted alkyl group); δ represents a residue necessary for completing a fused benzene ring.

Specific examples of this type of CAR are U.S. Pat.Nos. 4,198,235, 4,179,291, 4,273,855, and British Patent 2,090,99
It is described in Issue 0A.

Further, CAR suitable for this type of compound includes a group represented by formula (YV).

Wherein, Ball has the same meaning as in formula (YI), epsilon is an oxygen atom or = NG ³² group (G ³² represents an amino group which may have a hydroxyl group or a substituent), at that time H ₂ N−G
Examples of the compound ³² include hydroxylamine, hydrazines, semicarbazides, thiosemicarbazides and the like, wherein β ″ is a 5-, 6- or 7-membered saturated or unsaturated non-aromatic hydrocarbon. A group of atoms necessary to form a ring.

G ³¹ represents a hydrogen atom, a halogen atom such as fluorine, chlorine, or bromine. U.S. Pat.
149,829 and JP-A-54-48534.

Other examples of the CAR of this type of compound include, for example, U.S. Patent Nos. 3,493,939 and 3,628,952, and U.S. Pat.
Nos. 3,934 and 3,844,785 and the like.

Further, the CAR of the present invention includes a group represented by the formula (YVI).

In the formula, α is OR ⁴¹ or NHR ⁴² , R ⁴¹ is hydrogen or a hydrolyzable component, and R ⁴² is hydrogen or an alkyl group having 1 to 50 carbon atoms or a group capable of hydrolyzing NHR ^42. A ⁴¹ represents an atomic group necessary for forming an aromatic ring, Ball is an organic immobilizing group present on the aromatic ring, and Ball may be the same or different, and m is 1
Or an integer of 2.

X is a divalent organic group having 1 to 8 atoms, and a nucleophilic group (Nu) and an electrophilic center (* carbon atom) generated by oxidation form a 5- to 12-membered ring. Nu represents a nucleophilic group. n is an integer of 1 or 2. α is the above equation (Y
It is synonymous with I). A specific example of this type of CAR is disclosed in
No. 57-20735.

Further, another type of compound represented by the formula (I) releases a diffusible dye by, for example, self-cyclization in the presence of a base. However, when it reacts with an oxidized developer, the dye is substantially not released. Non-diffusible imaging compounds.

CARs useful for compounds of this type include, for example, those of the formula (YV
II).

In the formula, α ′ is an oxidizable nucleophilic group such as a hydroxyl group, a primary or secondary amino group, a hydroxyamino group, a sulfonamide group or a precursor thereof,
α ″ is a dialkylamino group or any of the groups defined as α ′, G ⁵¹ is an alkylene group having 1 to 3 carbon atoms, a represents 0 or 1, and G ⁵² represents 1 carbon atom. A substituted or unsubstituted alkyl group containing from 40 to 40;
Or a substituted or unsubstituted aryl group containing 6 to 40 carbon atoms, G ⁵³ is an electrophilic group such as —CO—, —CS—, and G ⁵⁴ is an oxygen atom, a sulfur atom, a selenium atom, A nitrogen atom or the like, and when it is a nitrogen atom, a hydrogen atom, an alkyl group or a substituted alkyl group containing 1 to 10 carbon atoms,
It may be substituted with an aromatic residue containing 6 to 20 carbon atoms.

G ⁵⁵ , G ⁵⁶ and G ⁵⁷ are each a hydrogen atom, a halogen atom,
Carbonyl group, Surufuamiru group, a sulfonamido group, are those of the alkyl group or G ⁵² synonymous containing 1 to 40 carbon atoms, G ⁵⁵ and G ⁵⁶ may together form a 5- to 7-membered ring .

G ⁵⁶ May be used. However, at least one of G ⁵² , G ⁵⁵ , G ⁵⁶ and G ⁵⁷ represents a ballast group. A specific example of this type of CAR is described in U.S. Pat. No. 4,108,850.

Suitable CARs for this type of compound are further represented by the formula (Y VII
I) and (Y IX).

Nu ⁶¹ and Nu ⁶² may be the same or different and represent a nucleophilic group or a precursor thereof, and Z ⁶¹ is an electronegative 2 carbon atom substituted by R ⁶⁴ and R ^65.
Each of R ⁶¹ , R ⁶² and R ⁶³ represents hydrogen,
A halogen, an alkyl group, an alkoxy group or an acylamino group, or R ⁶¹ and R ⁶² form a condensed ring with the rest of the molecule when adjacent to the ring, or R ⁶² and R ⁶³ are condensed with the rest of the molecule Form a ring, R ⁶⁴ and R ⁶⁵
Each may be the same or different and represents a hydrogen, a hydrocarbon group, or a substituted hydrocarbon group, and a substituent R ⁶¹ ,
A ballast group (Ball) of sufficient size in at least one of R ⁶² , R ⁶³ , R ⁶⁴ or R ⁶⁵ is present to render the compound immobile. A specific example of this type of Y is described in British Patent No.
No. 1,593,669 and U.S. Pat. No. 4,232,107.

Suitable CARs for this type of compound further include those of formula (YX)
There is a group represented by

In the formula, Ball and β ′ are the same as those of the formula (Y II), and G ⁷¹ represents an alkyl group (including a substituted alkyl group). For specific examples of this type of Y, see US Pat. No. 3,928,
Nos. 678 and 4,199,355.

Another type of compound of formula (I) is a non-diffusible image-forming compound that does not itself release a dye but releases a dye when reacted with a reducing agent.
In this case, it is preferable to use a compound that mediates the redox reaction (so-called electron donor) in combination.

CARs useful for compounds of this type include, for example, those of the formula (YX
And groups represented by I).

In the formula, Ball and β ′ are the same as those of the formula (YII), and G ⁷¹ is an alkyl group (including a substituted alkyl group). For a specific example of this type of CAR, see U.S. Pat.
Nos. 2,891, 4,139,379 and 4,218,368.

CARs suitable for this type of compound further include the group represented by (YX II).

A specific example of this CAR is described in U.S. Pat.
No. 4,356,249 and No. 4,358,525.

Suitable CARs for this type of compound are further represented by the formula (YX III
A) and (YX III B).

(However, (Nu _OX ) ¹ and (Nu _OX ) ² may be the same or different and each represents an oxidized nucleophilic group,
Other symbols are as defined in the formulas (Y VIII) and (Y IX). ) Specific examples of this type of CAR are described in U.S. Patent Nos. 4,232,107 and 4,371,684.

The patents cited in YX I, YX II, YX III and YX III B describe the combined use of electron donors.

Also, as more preferred, EP 220,746A
No. 2, U.S. Pat.No. 4,783,396, Published Technical Report 87-6199, JP-A-63-201653, JP-A-63-201654, and the like, each having an NX bond (X represents oxygen, sulfur or nitrogen) in one molecule. Represents an atom)
With a compound having an electron attractive SL, compounds SO ₂ -X (X is as defined above) in one molecule described in Japanese Patent Application Sho 62-106885 having an electron attractive group, No. Sho 63-271344 Compound having a PO-X bond (X is as defined above) and an electron-withdrawing group in one molecule described in JP-A-63-271341, and a C-X 'bond (Min. X ′ has the same meaning as X or —SO ₂
Represents a compound having an electron-withdrawing group.

Particularly preferred as this type of CAR are those of the formula (YX
IV). Specific examples of the CAR are described in U.S. Pat. No. 4,783,396, but a compound represented by the formula (YXV) is particularly preferably used in the present invention.

In the formula, EAG represents a group that receives an electron from a reducing substance. N and O represent a nitrogen atom and an oxygen atom, respectively. R ⁸¹ and R ⁸² represent a substituent other than a hydrogen atom. When R ⁸¹ or R ⁸² is bonded to Time _t , it represents a mere bond or a substituent other than a hydrogen atom. R ⁸¹ and R ⁸²
May combine with each other to form a ring.

X is -O-, -S- or (R ⁶ is as defined above). Particularly, -O- is preferable.

Time represents a group that releases Dye via a subsequent reaction, triggered by the cleavage of the fossil-oxygen-double bond in the formula,
t represents 0 or 1. In the formula, a solid line indicates a bond, and a broken line indicates that at least one is bonded.

In the formula, R ⁸³ and R ⁸⁴ are each a mere bond, a hydrogen atom or a group capable of substituting the same, and may be mutually bonded to form a saturated or unsaturated carbocyclic or heterocyclic ring. The general formulas (YX IV) and (YX V) are R ^{81 to} R ⁸⁴ or E
It is preferred to have a ballast group at the position of AG.

The ballast group in the general formulas (YI) to (YXV) is an organic ballast group capable of rendering the dye image forming compound of the general formula (I) non-diffusible, and is a hydrophobic group having 8 to 32 carbon atoms. It is preferably a group containing a functional group. Such an organic ballast group may be directly or directly linked to a dye image forming compound (for example, an imino bond, an ether bond, a thioether bond, a carbonamide bond, a sulfonamide bond, a ureido bond, an ester bond, a carbamoyl bond, a sulfamoyl bond, etc.). Combinations).

Hereinafter, specific examples of the compound of the general formula (I) used in the present invention are shown, but the present invention is not limited thereto.

Next, specific synthesis examples of the synthesis method of the present invention are shown below.

Synthesis Example Synthesis of Compound 1 8.6 g of Compound A ^* was dissolved in 50 ml of dimethylacetamide, and 3 ml of pyridine was added dropwise under ice cooling. After stirring at 0 ° C. for 10 minutes, 5.0 g of 5-amino-4- (chlorosulfonyl-2,5-dichlorophenylazo) -3-methyl-1-phenyl-pyrazole was added as a powder and stirred at room temperature for 5 hours. did. After the completion of the reaction, the reaction mixture was poured into dilute aqueous hydrochloric acid and extracted with ethyl acetate. The extract was washed with diluted hydrochloric acid and water and dried, and ethyl acetate was distilled off under reduced pressure.

The residue was subjected to silica gel flash column chromatography to obtain the target compound from a mixed solvent fraction of ethyl acetate / hexane 5: 1, and then recrystallized from a mixed solvent of acetone / methanol 1: 3 to obtain Compound 1. .

Yield 10.5g Yield 84.6% Compound A ^* The image forming compound in the present invention can be used alone, but a reducing substance that reduces exposed silver halide and cross-oxidizes with the compound of the present invention can be used in combination. As the reducing substance, various substances can be used. Preferably, hydroquinones, 3-pyrazolidones, aminophenols, catechols, p-phenylenediamines, aminonaphthols, catechols,
p-Phenylenediamines, aminonaphthols, reductones and the like.

In addition, a precursor that hydrolyzes under alkaline conditions to generate the above-described reducing compound can also be used.

For example, it is disclosed in JP-A-55-52055, JP-B-54-39727, and JP-A-57-135949.

Specific examples of the more preferable reducing compound include the following compounds.

3-pyrazolidones, for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 1-m- Tolyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-
Phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4,
4-bis- (hydroxymethyl) -3-pyrazolidone,
1,4-di-methyl-3-pyrazolidone, 4-methyl-3
-Pyrazolidone, 4,4-dimethyl-3-pyrazolidone,
1- (3-chlorophenyl) -4-methyl-3-pyrazolidone, 1- (4-chlorophenyl) -4-methyl-3
-Pyrazolidone, 1- (4-tolyl) -4-methyl-3
-Pyrazolidone, 1- (2-tolyl) -4-methyl-3
-Pyrazolidone, 1- (4-tolyl) -3-pyrazolidone 1- (3-tolyl) -3-pyrazolidone, 1- (3-
Tolyl) -4,4-dimethyl-3-pyrazolidone, 1-
(2-trifluoroethyl) -4,4-dimethyl-3-pyrazolidone, 5-methyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-stearoyloxymethyl- 3-pyrazolidone, 1-phenyl-4-methyl-4-uraroyloxymethyl-3-pyrazolidone, 1-phenyl-4,4-bis- (lauroyloxymethyl) -3-pyrazolidone,
-Phenyl-2-acetyl-3-pyrazolidone, 1-phenyl-3-acetoxypyrazolidone; hydroquinones such as hydroquinone, toluhydroquinone, 2,6
-Dimethylhydroquinone, t-butylhydroquinone, 2,5-di-tbutyl-hydroquinone, t-octylhydroquinone, 2,5-di-t-octylhydroquinone, pentadecylhydroquinone, 5-pentadecylhydroquinone-2-sulfonic acid Sodium, p-benzoyloxyphenol, 2-methyl-4-benzoyloxyphenol, 2-t-butyl-4- (4-chlorobenzoyloxy) phenol and the like; aminophenols such as 4-amino-2,6-dichloro Phenol, 4
-Amino-2,6-dibromophenol, 4-amino-2
-Methylphenol sulphate, 4-amino-3-methylphenol sulphate, 4-amino-2,6-dichlorophenol hydrochloride, p-aminophenol, p-methylaminophenol, p-dimethylaminophenol, p-dimethyl Aminophenol, p-dibutylaminophenol, p-piperidinoaminophenol, 4-dimethylamino-2,6-dimethoxyphenol and the like; phenylenediamines such as N-methyl-p-
Phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine,
N, N, N ', N'-tetramethyl-p-phenylenediamine, 4-diethylamino-2,6-dimethoxyaniline and the like; reductones such as piperidinohexose reductone, pyridinohexose reductone and the like .

In addition, Research Disclosure Magazine No. 151 No. 1510
8, U.S. Pat.No. 4,021,240 includes 2,6-dichloro-4-
Substituted sulfonamidophenol, 2,6-dibromo-4-
Substituted sulfonamidophenols, p- (N, N-dialkylaminophenol) sulfamine, etc. are described in JP-A-59-116740 and are effective. In addition to the above phenol-based reducing agents, naphthol-based reducing agents such as 4-aminonaphthol derivatives and 4-substituted sulfonamidonaphthol derivatives are useful.

These reducing substances or their pre-driving bodies can be used alone or in combination of two or more.

Silver halide that can be used in the present invention includes silver chloride, silver bromide, silver iodide, or silver chlorobromide, silver chloroiodide, silver iodobromide,
Any of silver chloroiodobromide may be used. The halogen composition inside the grains may be uniform, or the grains may have a multiple structure having different compositions on the surface and inside (Japanese Patent Application Laid-Open Nos. 57-154232 and 58-10).
Nos. 8533, 59-48755, 59-52237, U.S. Pat.
433,048 and EP 100,984). Further, tabular grains having a grain thickness of 0.5 μm or less, a diameter of at least 0.6 μm and an average aspect ratio of 5 or more (US Pat. No. 4,414,31)
0, 4,435,499 and West German Open Patent (OLS) 3,24
1,646A1) or monodisperse emulsions having a nearly uniform particle size distribution (JP-A-57-178235, JP-A-58-100846, JP-A-58-100846).
-14829, WO 83 / 02338A1, EP 64,412A
3 and 83,377 A1) can also be used in the present invention. Two or more silver halides having different crystal habits, halogen compositions, grain sizes, grain size distributions and the like may be used in combination. Two or more types of monodispersed emulsions having different grain sizes may be mixed to adjust the gradation.

The grain size of the silver halide used in the present invention is preferably an average grain size of 0.001 μm to 10 μm, more preferably 0.001 μm to 10 μm.
Those having a size of from 5 μm to 5 μm are more preferred. These silver halide emulsions may be prepared by any of an acidic method, a neutral method, and an ammonia method. The reaction between the soluble silver salt and the soluble halide may be a one-sided mixing method, a simultaneous mixing method, Or any of the following compositions: An inverse mixing method in which grains are formed in excess of silver ions, or a controlled double jet method in which pAg is kept constant can also be employed. Further, in order to accelerate the grain growth, the addition concentration, the addition amount or the point angular velocity of the added silver salt and halogen salt may be increased (JP-A-55-142329, JP-A-55-158124, U.S. Pat. No. 3,650,757). etc).

Epitaxy-bonded silver halide grains can also be used (JP-A-56-16124, U.S. Pat. No. 4,094,6).
No. 84).

In the step of forming the silver halide grains used in the present invention, ammonia is used as a silver halide solvent,
No. 386, organic thioether derivatives described in
Sulfur-containing compounds described in JP-A-14439 can be used.

Cadmium salts, zinc salts, lead salts, thallium salts, and the like may coexist in the process of particle formation or physical ripening.

Further, a water-soluble iridium salt such as iridium chloride (III, IV) or ammonium hexachloroiridate, or a water-soluble rhodium salt such as rhodium chloride can be used for the purpose of improving high illuminance failure and low illuminance failure.

The soluble salts may be removed from the silver halide emulsion after the formation of the precipitate or after the physical ripening. Therefore, the silver halide emulsion can be subjected to the Nudel washing method or the sedimentation method.

The silver halide emulsion may be used as it is after unripe, but usually it is used after chemical sensitization. A known sulfur sensitization method, reduction sensitization method, noble metal sensitization method, or the like can be used alone or in combination for an emulsion for a normal photosensitive material. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-58-126526 and JP-A-58-215644).

The silver halide emulsion used in the present invention may be a surface latent image type in which a latent image is mainly formed on the grain surface or an internal latent image type in which a latent image is formed inside the grain. Direct reversal emulsions combining an internal latent image type emulsion with a nucleating agent and / or light fogging can also be used. Internal latent image type emulsions suitable for this purpose are described in U.S. Pat.Nos. 2,592,250 and 3,761,2
No. 76, JP-B-58-3534 and JP-A-57-136641. Preferred nucleating agents for combination in the present invention are U.S. Patent Nos. 3,227,552 and 4,245,037.
No. 4,255,511, No. 4,266,031, No. 4,276,36
No. 4 and OLS No. 2,635,316. Optical fogging is described in JP-B-45-12710 and JP-A-61-15964.
A known method according to No. 1 or the like can be used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes or the like.

Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, that is, an isodrenine nucleus,
Benzisodrenine nucleus isodol nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus,
A naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

In a merocyanine dye or a complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-
A 5- to 6-membered heterocyclic nucleus such as a 2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, aminostyryl compounds substituted with a nitrogen-containing heterocyclic group (for example, those described in U.S. Pat. Nos. 2,933,390 and 3,635,721), and aromatic organic acid formaldehyde condensates (for example, U.S. Pat. No. 3,743,510, etc.) Listed)),
Cadmium salts, azaindene compounds and the like may be included. U.S. Pat.Nos. 3,615,613, 3,615,641, 3,
The combinations described in 617,295 and 3,635,721 are particularly useful.

Gelatin is advantageously used as a binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin is lime-treated,
Either one treated with an acid may be used. The details of the method for producing gelatin are described in The Macromolecule Chemistry of Gelatin, by Arthur Wuice (Agademick Press, 1964).

The photographic emulsion used in the present invention may contain a surfactant alone or as a mixture.

Although they are used as coating aids, they are sometimes applied for other purposes, such as emulsification and dispersion, improvement of sensitized photographic properties, antistatic and anti-adhesion.
These surfactants are natural surfactants such as saponin,
Nonionic surfactants such as alkylene oxides, glycenes and glycidols, higher alkylamines, quaternary ammonium salts, pyridines and other heterocycles, cationic surfactants such as phosphonium or sulfoniums, carboxylic acids, sulfonic acids , Anionic surfactants containing acidic groups such as phosphoric acid, sulfate ester groups and phosphate ester groups, amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric acid or phosphate esters of amino alcohols.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines Thioindole compounds such as oxazolinethione; azaindenes; triazaindenes; tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7-tetraazaindenes), pentaazaindenes and the like; Many compounds known as antifoggants or stabilizers, such as benzenethiosulfins, benzenesulfinic acid, benzenesulfonamide, and the like, can be added.

The photographic emulsion layer of the photographic light-sensitive material of the present invention may contain, for example, thioether compounds, thiomorpholins, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, and 3-pyrazolidones for the purpose of increasing the sensitivity, increasing the contrast, or promoting development. And the like.

In the photographic light-sensitive material used in the present invention, for the purpose of improving the dimensional stability of the photographic emulsion layer and other hydrophilic colloid layers,
It may include a dispersion of a water-insoluble or poorly soluble synthetic polymer. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene or the like alone or in combination, or acrylic acid, Methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate,
A polymer having a combination of a sulfoalkyl (meth) acrylate, styrene sulfonic acid and the like as a monomer component can be used.

Various other additives may be used in the silver halide photographic light-sensitive material of the present invention. For example, hardeners, brighteners, dyes, desensitizers, coating aids, antistatic agents, plasticizers, sliding agents, matting agents, development accelerators, mordants, ultraviolet absorbers, anti-fading agents, and color fog prevention Agents and the like.

About these additives, specifically, RESEARCH DISCLOSURE 176 No. 22-3
One described on page 1 (RD-17643) (Dec, 1987) can be used.

The compounds of the general formula (I) of the present invention capable of releasing a diffusible dye are described, for example, in JP-A-58-149046, JP-A-59-154445,
No. 59-165054, No. 59-180548, No. 59-218443, No.
Nos. 60-133449, U.S. Pat.Nos. 4,503,137 and 4,474,867
No. 4,483,914, No. 4,455,363, No. 4,500,62
No. 6, a movable dye is formed by thermal development described in JP-A-60-79709 and the like, and the dye is preferably used for a photothermographic material utilizing silver halide for transferring the dye to a dye fixing layer. . In the following, the photothermographic material may be referred to as a photosensitive element.

When applied to a photothermographic element, an organic metal salt can be used in combination with the photosensitive silver halide as an oxidizing agent. Among such organic metal salts, an organic silver salt is particularly preferably used.

Examples of the organic compound that can be used to form the above-mentioned organic silver salt oxidizing agent include benzotriazoles, fatty acids and other compound parts described in U.S. Pat. No. 4,500,626, columns 52-53. Also useful are silver salts of carboxylic acids having an alkyl group such as silver phenylpropiolate described in JP-A-60-113235 and acetylene silver described in JP-A-61-249044. Two or more organic silver salts may be used in combination.

The above organic silver salts can be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of the photosensitive silver halide. The total coating amount of the photosensitive silver halide and the organic silver salt is suitably from 50 mg to 10 g / m ² in terms of silver.

In the present invention, various antifoggants or photographic stabilizers can be used. An example is RD17643
(1978) Azoles and azaindenes described on pages 24 to 25, carboxylic acids and phosphoric acids containing nitrogen described in JP-A-59-168442, or mercapto compounds and metals thereof described in JP-A-59-111636 Salts and acetylene compounds described in JP-A-62-87957 are used.

As the binder for the constituent layers of the photosensitive element and the dye fixing element, hydrophilic binders are preferably used. Examples thereof include those described on pages (26) to (28) of JP-A-62-253159. Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, polyvinyl alcohol, Examples include polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M (M
Is a homopolymer of a vinyl monomer having a hydrogen atom or an alkali metal) or a copolymer of the vinyl monomers or other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-manufactured by Sumitomo Chemical Co., Ltd.) 5H) is also used. These binders can be used in combination of two or more kinds.

When a system for performing thermal development by supplying a small amount of water is used, it is possible to quickly absorb water by using the above superabsorbent polymer. Further, when the superabsorbent polymer is used for the dye fixing layer and its protective layer, it is possible to prevent the dye from being re-transferred from the dye fixing element to another after transfer.

In the present invention, the coating amount of the binder is 1 m ² per 20g
The following is preferable, and particularly, it is suitably 10 g or less, more preferably 7 g or less.

The constituent layers (including the backing layer) of the photosensitive element or the dye-fixing element include various polymers for the purpose of improving the physical properties of the film such as dimensional stability, curl prevention, adhesion prevention, film crack prevention and pressure increase / decrease sensation. Latex can be included. Specifically, JP-A Nos. 62-245258, 62-136648, 62
Any of the polymer latexes described in JP-110066 or the like can be used. In particular, when a polymer latex having a low glass transition point (40 ° C. or less) is used for the mordant layer, cracking of the latent layer can be prevented, and when a polymer latex having a high glass transition point is used for the back layer, curling can be prevented. The prevention effect is obtained.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. In addition, a dye-donating compound having a reducibility described later is included (in this case, another reducing agent may be used in combination). Also,
It is also possible to use a reducing agent precursor which does not itself have a reducing property but finds a reducing property by the action of a nucleophile or heat during the development process.

Examples of reducing agents used in the present invention include U.S. Pat.
Columns 49-50 of 4,500,626, 30-31 of 4,483,914
No. 4,330,617, 4,590,152, JP-A-60-14
Nos. 17- (18), Nos. 57-40245 and 56-1 of No. 0335
38736, 59-178458, 59-53831, 59-1824
No. 49, No. 59-182450, No. 60-119555, No. 60-128436
No. to No. 60-128439, No. 60-198540, No. 60-18
No. 1742, No. 61-259253, No. 62-244044, No. 62-1312
From No. 53 to No. 62-131256, there are reducing agents and reducing agent precursors described in EP 220,746 A2, pp. 78-96.

Combinations of various reducing agents can also be used, such as those disclosed in U.S. Pat. No. 3,039,869.

When a diffusion-resistant reducing agent is used, an electron transfer agent and / or a male transfer agent may be used, if necessary, to promote electron transfer between the diffusion-resistant reduction agent and the developable silver halide. Precursors can be used in combination.

The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors.
It is desirable that the mobility of the electron transfer agent or its precursor is higher than that of the diffusion-resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any one that does not substantially move in the layer of the photosensitive element among the reducing agents described above, and is preferably a hydroquinone, Examples thereof include sulfonamide phenols, sulfonamido naphthols, compounds described as electron donors in JP-A-53-110827, and dye-donating compounds having diffusion resistance and reducing property described later.

In the present invention, the amount of the reducing agent added is based on 1 mole of silver.
It is 0.01 to 20 mol, particularly preferably 0.1 to 10 mol.

In the present invention, a compound for stabilizing an image simultaneously with activation of development can be used in the photosensitive element. Specific compounds preferably used are described in U.S. Pat.
No. 626, columns 51-52.

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a photosensitive element. The dye-fixing element may be coated separately on a support separate from the photosensitive element, or may be coated on the same support as the photosensitive element. As for the relationship between the photosensitive element and the dye-fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationships described in column 57 of US Pat. No. 4,500,626 can be applied to the present invention.

The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the field of photography can be used, and specific examples thereof are described in U.S. Pat.
-88256, mordants described on pages (32) to (41);
Nos. 2-244043 and 62-244036. Further, a dye-receiving polymer compound as described in US Pat. No. 4,463,079 may be used.

The dye-fixing element may be provided with an auxiliary layer such as a protective layer, a release layer, and an anti-curl layer, if necessary. It is particularly useful to provide a protective layer.

The constituent layers of the photosensitive element and the dye fixing element include a plasticizer,
A high-boiling organic solvent can be used as a slipping agent or an agent for improving the releasability of the photosensitive element and the dye fixing element. Specific examples include those described in JP-A-62-253159, page (25) and JP-A-62-245253.

Further, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. Examples thereof include various modified silicone oils described in “Modified Silicone Oil” Technical Data P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name: X-22-37).
10) is effective.

Also, silicone oils described in JP-A-62-215953 and Japanese Patent Application No. 62-23687 are effective.

An anti-fading agent may be used in the photosensitive dye or the dye fixing element. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective.

Examples of ultraviolet absorbers include benzotriazole-based compounds (US Pat. No. 3,533,794, etc.), 4-thiazolidone-based compounds (US Pat. No. 3,352,681), benzophenone-based compounds (JP-A No. 46-2784, etc.), and others. JP-A-54-
There are compounds described in JP-A-48535, JP-A-62-136641 and JP-A-61-88256. Further, an ultraviolet absorbing polymer described in JP-A-62-260152 is effective.

As metal complexes, U.S. Pat.Nos. 4,241,155 and 4,2
Nos. 45,018, columns 3-36, 4,254,195, columns 3-8, JP-A-62-174741 and JP-A-61-88256, pages (27) to (29),
Japanese Patent Application Nos. 62-234103 and 62-31096, Japanese Patent Application No. 62-23059
There are compounds described in No. 6, etc.

Examples of useful anti-fading agents are described in JP-A-62-215272 (125).
~ (137).

An anti-fading agent for preventing fading of the dye transferred to the dye-fixing element may be contained in the dye-fixing element in advance, or may be supplied to the dye-fixing element from outside such as a photosensitive element. .

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination with each other.

A fluorescent whitening agent may be used in the light-sensitive element and the dye-fixing element. In particular, it is preferable to incorporate a fluorescent brightening agent in the dye fixing element or to supply it from outside such as a photosensitive element. For example, K. Veenkataraman ed., "The Chemistry of Synt
hetic Dyes, Vol. V, Chapter 8, and JP-A-61-143752. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given.

The optical brightener can be used in combination with a fading inhibitor.

Examples of the hardener used in the constituent layers of the photosensitive element and the dye-fixing element include U.S. Pat.
No. 5, 62-245261, 61-18942 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners Vinyl sulfone hardeners (such as N, N'-ethylene-bis (vinylsulfonylacetamide) ethane), N-methylol hardeners (such as dimethylol urea), or polymer hardeners (Japanese Patent Laid-Open No. Sho 62) -234157, etc.).

In the constituent layers of the photosensitive element and the dye fixing element, various surfactants can be used for the purpose of coating aid, improving releasability, improving slipperiness, preventing static charge, promoting development, and the like. Specific examples of the surfactant are described in JP-A Nos. 62-173463 and 62-183457.

The constituent layers of the light-sensitive element and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, and improving releasability. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8 to 17, JP-A-61-2094.
No. 4, No. 62-135826, hydrophobic surfactants such as fluorine-based surfactants described above, or oil-like fluorine-based compounds such as fluorine oil or solid fluorine-containing compound resins such as tetrafluoroethylene resin Fluorine compounds.

A matting agent can be used for the photosensitive element and the dye fixing element. Examples of the matting agent include compounds described in JP-A-61-88256 (page 29) such as silicon dioxide, polyolefin and polymethacrylate, and benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like. And No. 62-110065.

In addition, the constituent layers of the photosensitive element and the dye fixing element include:
A heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like may be included. Specific examples of these additives are disclosed in
No. 88256, pages (26) to (32).

In the present invention, an image formation accelerator can be used in the photosensitive element and / or the dye fixing element. Examples of the image formation accelerator include the promotion of a redox reaction between a silver salt oxidizing agent and a reducing agent, the promotion of a reaction such as the generation of a dye from a dye-providing substance or the decomposition or release of a diffusible dye, and the use of a photosensitive material layer. From the physicochemical function to bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, silver Or, it is classified into a compound having an interaction with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. See U.S. Pat.
No. 9, columns 38-40.

Examples of the base precursor include salts of an organic acid and a base that are decarboxylated by heat, compounds that release amines by an intramolecular nucleophilic substitution reaction, Rothsen rearrangement or Beckmann rearrangement, and the like. Specific examples thereof are described in U.S. Pat.
-65038 and the like.

In a system in which thermal development and transfer of a dye are carried out simultaneously in the presence of a small amount of water, it is preferable to include a base and / or a base precursor in the dye-fixing element from the viewpoint of improving the storage stability of the photosensitive element.

In addition to the above, a combination of a sparingly soluble metal compound described in European Patent Publication No. 210,660 and a compound capable of forming a complex with a metal ion constituting the sparingly soluble metal compound (referred to as a complex forming compound); Compounds that generate a base by an electric field described in 61-232451 can also be used as a base precursor. In particular, the former method is effective. The sparingly soluble metal compound and the complex forming compound are advantageously added separately to the light-sensitive element and the dye-fixing element.

In the light-sensitive element and / or dye-fixing element of the present invention, various development terminators can be used for the purpose of always obtaining a constant image with respect to fluctuations in processing temperature and processing time during development.

As used herein, the term "development terminator" refers to a compound that neutralizes a base or reacts with a base immediately after appropriate development to reduce the base concentration in the film and to stop development by interacting with a compound or silver and silver salt to suppress development. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. More specifically, JP-A-62-253159 (31) to (32)
Page.

As the support of the photosensitive element or dye fixing element of the present invention,
Those that can withstand the processing temperature are used. Generally, paper and synthetic polymers (films) are mentioned. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetylcellulose), or films containing pigments such as titanium oxide, and polypropylene. Synthetic paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass, etc. are used. .

These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene.

In addition, the supports described in JP-A-62-253159, pages (29) to (31) can be used.

The surface of these supports may be coated with a hydrophilic binder, a semiconductor metal oxide such as alumina sol or tin oxide, carbon black or another antistatic agent.

The method of exposing and recording an image on the photosensitive element includes, for example, a method of directly photographing a landscape or a person using a camera, a method of exposing through a reversal film or a negative film using a printer or a enlarger, and a method of copying machine. Scanning and exposing the original image through slits using an exposure device, etc., exposing the image information by emitting light from a light emitting diode, various lasers, etc. via electrical signals, CRT, liquid crystal display, electroluminescence There is a method of outputting to an image display device such as a sense display or a plasma display and exposing directly or via an optical system.

As the light source for recording an image on the photosensitive element, as described above, natural light, a tungsten lamp, a light emitting diode, a laser light source, a U.S. Pat.
The light sources described in the column can be used.

The image information includes an image signal obtained from a video camera, an electronic still camera, and the like, a television signal represented by the Nippon Television System (NTSC), and an image obtained by dividing an original image into a number of pixels such as a scanner. An image signal created using a computer represented by a signal, CG, or CAD can be used.

(Specific Action and Effect of the Invention) According to the present invention, since the image forming compound represented by the general formula (I) is contained, a yellow dye image which is stable to heat and light and has a high density can be quickly obtained. Color photosensitive material that can be used. Further, according to the present invention, it is possible to obtain a color light-sensitive material which has an excellent hue and gives an excellent yellow dye image with little change in hue over a wide pH range.

(Specific Examples of the Invention) Hereinafter, specific examples of the present invention will be described, and the effects of the present invention will be described in more detail.

Example 1 First, a method for producing a dye-fixing material will be described.

63 g of gelatin and 130 g of a mordant having the following structure were dissolved in 1300 ml of water and 45 μm on a polyethylene terephthalate support.
And then dried.

mordant Further, a solution prepared by dissolving 35 g of gelatin and 1.05 g of 1,2-bis (vinylsulfonyl acetamidaethane) in 800 ml of water was applied thereon so as to have a wet film thickness of 17 μm, dried and dried to obtain a dye fixing material D-1. made.

Next, the following yellow dye YA (dye portion of the compound of the present invention) and YB (comparative compound) in DMF / 2% sodium hydrogen carbonate 1/10 aqueous solution The above-mentioned dye fixing material D-1 was immersed until the transmission density reached 1.0, washed with distilled water for 10 seconds, and dried to prepare Samples 101 and 102.

Next, the light resistance of the dye was evaluated using this sample. Light fastness test was 17,000 lux fluorescent light (no UV filter)
The results are expressed as the irradiation time until the concentration reaches 0.9.

From the above results, the dye moiety (Y-
It can be seen that A) is an excellent dye portion having higher light resistance than the highly stable pyrazoloin yellow dye (YB) generally used in the diffusion transfer method.

Example 2 Gelatin dichromate hardener on a glass substrate (coated with a gelatin photosensitive solution (including ammonium bichromate), irradiated with a mercury lamp over the entire surface, washed with water and dried to a dry film thickness of 1.2 μm)
Using an aqueous solution of the following water-soluble yellow dye YC (dye of the compound of the present invention) and YD (comparative substance)
Samples 201 and 202 stained to 1.0 were produced.

Next, the heat resistance of the dye was evaluated using this sample.

The heat resistance test was performed using a 180 ° C. oven. The concentration after 3 hours is shown below.

As is clear from the above results, the dye portion in the compound of the present invention is an excellent dye portion having considerably higher heat resistance than the pyrazolone yellow dye generally used in the diffusion transfer method.

Similar experiments were conducted for some 5-aminopyrazole azo dyes other than YC, but showed similar high heat resistance.

Example 3 A color photosensitive material 301 having a multilayer structure as shown in Table 1 was prepared.

This section describes how to prepare silver halide emulsions for the fifth layer and the first layer.

A well-stirred aqueous gelatin solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 ml of water and kept at 75 ° C.) is combined with 600 ml of an aqueous solution containing sodium chloride and potassium bromide and an aqueous silver nitrate solution (600 ml of water is mixed with silver nitrate). 0.59 mol) was added at the same flow rate over the course of 40 minutes. Thus, a monodisperse cubic silver chlorobromide emulsion (50 mol% of bromine) having an average grain size of 0.40 μm was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added, followed by chemical sensitization at 60 ° C. 60 emulsion yield
It was 0g.

Next, how to prepare a silver halide emulsion for the third layer will be described.

A well-stirred aqueous gelatin solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 ml of water and kept at 75 ° C.) is combined with 600 ml of an aqueous solution containing sodium chloride and potassium bromide and an aqueous silver nitrate solution (600 ml of water is mixed with silver nitrate). 0.59 mol) was added at the same flow rate over the course of 40 minutes. Thus, a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.35 μm (80 mol% of bromine) was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added, followed by chemical sensitization at 60 ° C. 60 emulsion yield
It was 0g.

Next, how to prepare a gelatin dispersion of the image forming compound will be described.

5 g of the yellow image forming compound (36) of the present invention, 0.3 g of the following antifoggant ^*, and succinic acid 2-
0.5 g of sodium ethylhexyl ester sulfonate and 10 g of triisononyl phosphate were added, and 30 ml of ethyl acetate was added. The solution was heated and dissolved at about 60 ° C. to obtain a uniform solution. After stirring and mixing this solution and 100 g of a 10% solution of lime-processed gelatin,
The mixture was dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a yellow image-forming compound dispersion.

Using magenta image forming compound (1) and cyan image forming compound (2), a dispersion of magenta and cyan image forming compounds was prepared in the same manner as described above.

 Next, how to make an organic silver salt is described.

Organic silver salt (1) A method for preparing a silver benzotriazole emulsion will be described.

28 g of gelatin and 13.2 g of benzotriazole were dissolved in 300 ml of water. This solution was kept at 40 ° C. and stirred. A solution prepared by dissolving 17 g of silver nitrate in 100 ml of water was added to this solution over 2 minutes.

The pH of the benzotriazole silver emulsion was adjusted, allowed to settle, and excess salts were removed. Thereafter, the pH was adjusted to 6.30 to obtain a silver benzotriazole emulsion with a yield of 400 g.

Organic silver salt (2) 20 g of gelatin and 5.9 g of 4-acetylaminophenylpropiolic acid were dissolved in 1000 ml of a 0.1% aqueous sodium hydroxide solution and 200 ml of ethanol.

 This solution was kept at 40 ° C. and stirred.

To this solution, a solution prepared by dissolving 4.5 g of silver nitrate in 200 ml of water was added over 5 minutes.

The pH of the dispersion was adjusted and settled to remove excess salts. Thereafter, the pH was adjusted to 6.3 to obtain a dispersion of the organic silver salt (2) in a yield of 300 g.

The dye-fixing material was prepared as a dye-fixing material D-2 except that the support of D-1 in Example 1 was replaced with paper laminated with polyethylene.

G, R, IR tricolor separation filters (G is 500 to 600 nm, R is 600 to 700 nm bandpass filter, and the density is continuously changed) using a tungsten light bulb as a color light-sensitive material having the above multilayer structure. Was constructed using a filter having a transmittance of 700 nm or more) and exposed at 500 lux for 1 second.

Thereafter, the mixture was uniformly heated on a heat block heated to 140 ° C. for 30 seconds.

Next, 20 ml of water per 1 m ² was supplied to the film surface side of the dye-fixing material, and then the heat-treated photosensitive coating materials were overlapped with the fixing material such that the film surfaces were in contact with each other.

After heating on a heat block at 80 ° C for 6 seconds, the dye-fixing material was peeled off from the photosensitive material.
Corresponding to the three color separation filters of yellow,
Magenta and cyan color images were obtained.

The maximum density (Dmax.) And (Dmin.) Of each color were measured using a Macbeth reflection densitometer (RD-519). Table 5 shows the results.

It can be seen that the yellow image forming compound of the present invention gives a sufficient image.

Example 4 A photosensitive material 401 having the structure shown in the following table was prepared.

Water-soluble polymer (1) ^* Sumikagel L-5 (H) Water-soluble polymer (2) manufactured by Sumitomo Chemical Co., Ltd. ^* Surfactant (1) ^* Aerosol OT Surfactant (2) ^* Surfactant (3) ^* Surfactant (4) ^* Hardener (1) ^* 1,2-bis (vinylsulfonyl acetamide) ethane High-boiling organic solvent (1) ^* Tricyclohexyl phospate Yellow dye-donating substance (1) Magenta dye donating substance (2) Cyan dye donating substance (3) Antifoggant (1) ^* Sensitizing dye D-22 (third layer) Sensitizing dye D-51 (first layer) Electron donor ED-1 Reducing agent ED-7 Electron reducing agent X-2 The method of preparing the emulsion (I) for the first layer will be described.

A well-stirred aqueous gelatin solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 ml of water and kept at 75 ° C.) in an aqueous solution containing 600 ml of sodium chloride and potassium bromide and an aqueous nitric acid solution (600 ml of water and 0.59 silver nitrate) Mol dissolved) at the same time over 40 minutes. Thus, a monodisperse cubic silver chlorobromide emulsion (80 mol% of bromine) having an average grain size of 0.35 μm was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added, followed by chemical sensitization at 60 ° C. The yield of the emulsion was 600 g.

 Next, how to prepare the emulsion (II) for the third layer will be described.

A well-stirred aqueous gelatin solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 ml of water and kept at 75 ° C.) is an aqueous solution containing 600 ml of sodium chloride and potassium bromide and an aqueous silver nitrate solution (600 ml of water and 0.59 silver nitrate). Mol) and the following dye solution (I)
It was added at an equal flow rate over 40 minutes. Thus, a monodispersed cubic silver chlorobromide emulsion (80 mol% of bromine) having a dye having an average particle size of 0.35 μm adsorbed thereon was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added, followed by chemical sensitization at 60 ° C. The yield of the emulsion was 600 g. Dye solution (I): 160 mg of sensitizing dye (D-22) dissolved in 400 ml of methanol.

Next, how to prepare the emulsion (III) for the fifth layer will be described.

A well-stirred aqueous gelatin solution (20 g of gelatin and ammonium dissolved in 1000 ml of water and kept at 50 ° C.) is mixed with 1000 ml of an aqueous solution containing potassium iodide and potassium bromide and an aqueous silver nitrate solution (1000 ml of water and 1 ml of silver nitrate). Mol dissolved) at the same time while keeping the pAg constant. Thus, a monodispersed octahedral silver iodobromide emulsion having an average grain size of 0.5 μm (5 mol% of iodine) was prepared.

After washing with water and desalting, 5 mg of chloroauric acid (tetrahydrate) and 2 mg of sodium thiosulfate were added, and sensitized with gold and sulfur at 60 ° C. The yield of the emulsion was 1 kg.

Next, a method of preparing a gelatin dispersion of a dye-providing substance will be described.

13 g of a yellow dye-donating substance (1), 6.5 g of a high-boiling organic solvent (1), 6.5 g of an electron donor (ED-11) and 37 ml of cyclohexanone were dissolved in 100 g of a 10% gelatin solution and sodium dodecylbenzenesulfonate. Was stirred and mixed with 60 ml of a 2.5% aqueous solution, and then dispersed at 10,000 rpm for 10 minutes with a homogenizer. This dispersion is referred to as a yellow dye-providing substance dispersion.

16.8 g of a magenta dye-donating substance (2), 8.4 g of a high boiling point organic solvent (1), and 6.3 g of an electron donor (ED-11) were added to and dissolved in 37 ml of cyclohexanone, and 100 g of a 10% gelatin solution and dodecylbenzene sulfone were added. 60 ml of 2.5% aqueous solution of sodium acid
After stirring and mixing, 10000r for 10 minutes with a homogenizer
Dispersed at pm. This dispersion is referred to as a magenta dye-providing substance dispersion.

15.4 g of a cyan dye-donating substance (3), 7.7 g of a high boiling point organic solvent (1) and 6.0 g of an electron donor (ED-11) were added to and dissolved in 37 ml of cyclohexanone, and 100 g of a 10% gelatin solution and dodecylbenzenesulfonic acid were added. After stirring and mixing with 60 ml of a 2.5% aqueous solution of soda, the mixture was dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a dispersion of a cyan dye-donating substance.

Yellow dye-donating substance (1) for the photosensitive material 401 described above.
Was replaced with the specific compound example (2) of the present invention, and a photosensitive material 402 prepared in exactly the same manner was also prepared.

 Next, a method of making the dye fixing material will be described.

Dye-fixing material R- is applied on a glass plate for liquid crystal color filter (Corning Fusion 7059) in the composition shown in the following table.
I made 3.

Silicone oil ^{* 1} Surfactant ^{* 2} Aerosol OT Surfactant ^{* 3 * 4} Polymer ^{* 5} Vinyl alcohol sodium acrylate copolymer (75/25 molar ratio) ^{* 7} Dextran (molecular weight 70,000) Mordant ^{* 6} High boiling organic solvent ^{* 8} Leofos 95 (manufactured by Ajinomoto Co., Inc.) Hardener ^{* 9} A tungsten light bulb was used as the color light-sensitive material having the above multilayer structure, and exposure was performed at 5,000 lux for 1/10 second through a color separation mosaic filter having B, G, R and black stripes.

While feeding the photosensitive material only with the exposure agent at a linear speed of 20 mm / sec, water of 12 ml / m ² was supplied to the emulsion surface with a wire bar, and immediately thereafter, the image receiving material and the film surface were superimposed so that the film surface was in contact with the emulsion surface.

The film was heated for 30 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film became 90 ° C. Next, when peeled off from the image receiving material, a clear image of blue, green, red, and black corresponding to the B, G, R and black color separation mosaic filters is formed on the image receiving material in any of the photosensitive materials 401 and 402. Was obtained without unevenness.

B, G, R and black color density (pixel center)
Are shown in the following table. It can be seen that the light-sensitive material (402) using the yellow color material of the present invention can form a sufficient color image even in this method.

The peak transmittance of each color (B, G, R) exceeded 70%.

Next, pass through yellow filters to photosensitive materials 401 and 402
After the entire surface was exposed at 5000 lux for 1/10 second, a transfer image was formed using the image receiving material R-3 in the same manner as above.

After washing with distilled water for 30 seconds and drying, each sample was compared for heat and light resistance.

The heat and light resistance test conditions are the same as in Examples 1 and 2,
Light irradiation is a result after one month, and heating is a result after three hours.

The numbers in the above table represent the ratio of the residual density at λ _max from the freshness. As in Examples 1 and 2, the image stability when the photosensitive element containing the compound of the present invention is used is clear. .

Example 5 A light-sensitive material 501 was prepared by removing the following composition from the light-sensitive material 402 shown in Example 4.

Further, an image receiving material R-4 was prepared by removing the following composition from the image receiving material R-3.

Using a tungsten light bulb for the color photosensitive material (501),
Exposure was performed at 5000 lux for 1/10 second through a mosaic filter (photomask) of B, G, R and black stripes. While feeding the exposed photosensitive material at a linear speed of 15 mm / sec, the emulsion surface was processed at 15 ml / m ² (10% guanidine carbonate + 0.5% sodium bicarbonate aqueous solution) and supplied with a wire bar, and immediately thereafter the image was received. Overlap the material R-4,
Adhere using a room temperature press, leave for 30 seconds, 90 ° C
And heated and transferred for another 30 seconds.

When 501 was peeled off from R-4, a mosaic color filter of B, G, R and black corresponding to a mosaic filter of B, G, R and black was obtained on the image receiving material (R-6).

Each pixel was B, G, and R with sufficient spectral absorption as a color filter, and there was no unevenness or defect.

Next, the color filter was washed with distilled water at 25 ° C. for 30 seconds, dried, and further coated with polyglycidyl methacrylate ^* (PGMA) of 1 μm by spin coating on the film surface of the image receiving material.
, And a strong protective film was formed by heat treatment.

Next, the upper portion of the color filter layer was covered with indium tin oxide (ITO) to form a common electrode.

 The formation method used ion plating.

Next, the ITO layer was covered with a polyimide film, and rubbing treatment was performed to form a liquid crystal alignment film.

On another substrate constituting the liquid crystal cell, an electrode having a pattern similar to that of the color filter was formed by a known method, and the wiring was further covered with an alignment film. The two types of substrates were bonded together, and liquid crystal was injected to prepare a liquid crystal cell.

The liquid crystal cell produced in this way was more satisfactory in brightness and durability (heat resistance and light resistance) as a display than a liquid crystal cell using a color filter by a dyeing method.

Claims (1)

(57) [Claims] 1. A light-sensitive element for a diffusion transfer method comprising, on a support, a light-sensitive silver halide emulsion layer combined with a yellow dye-donating compound represented by the following general formula (I). General formula [I] In the formula, CAR represents a carrier component capable of releasing a diffusible dye from the compound corresponding to or inversely corresponding to development under alkaline conditions. Link represents a group linking CAR and a diffusible dye, and m is 0 or 1. A broken line indicates that at least one of them is connected. R ¹ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a carbamoyl group, R ² represents an alkyl group, an aryl group, and R ³ represents an aryl group (Excluding aryl groups having a Hammett's σ _p value of less than 0.01).